Semiconductor device and method of manufacturing the same

ABSTRACT

A semiconductor device includes a lower electrode on a substrate, a capacitor dielectric layer on the lower electrode, and an upper electrode on the capacitor dielectric layer. The capacitor dielectric layer includes a base layer on the lower electrode and a dielectric particle layer in at least a portion of the base layer. The base layer includes a first dielectric material, and the dielectric particle layer extends at least partially continuously along a thickness direction of the capacitor dielectric layer and includes a second dielectric material different from the first dielectric material.

CLAIM OF PRIORITY

This application is a continuation application of and claims priorityfrom U.S. patent application Ser. No. 15/410,488, filed on Jan. 19,2017, which claims priority under 35 U.S.C. § 119 to Korean PatentApplication No. 10-2016-0068846 filed on Jun. 2, 2016 in the KoreanIntellectual Property Office, the disclosures of which are herebyincorporated by reference in its entirety.

BACKGROUND

1. Field

Example embodiments of the inventive concepts relate to semiconductordevices, and more specifically, to semiconductor devices includingcapacitor structures and methods of manufacturing the same.

2. Description of the Related Art

Due to higher integration and smaller sizes of semiconductor devices,the size of a capacitor of a DRAM device may also be reduced. Athickness of a capacitor dielectric layer between an upper electrode anda lower electrode is also reduced depending on the reduced size of thecapacitor. However, due to the reduced thickness of the capacitordielectric layer, a leakage current of the capacitor can be increasedand a short circuit between the upper electrode and the lower electrodeor a breakdown of the capacitor dielectric layer can occur.

SUMMARY

According to example embodiments of the inventive concepts, asemiconductor device may include a capacitor dielectric layer on thelower electrode, and an upper electrode on the capacitor dielectriclayer. The capacitor dielectric layer may include a base layer on thelower electrode and including a first dielectric material, and adielectric particle layer in at least a portion of the base layer. Thedielectric particle layer may at least partially continuously extendalong a thickness direction of the capacitor dielectric layer andincluding a second dielectric material different from the firstdielectric material.

According to example embodiments of the inventive concepts, asemiconductor device may include a lower electrode on a substrate, acapacitor dielectric layer on the lower electrode and having a surfaceroughness of 0.3 nm or less, and an upper electrode on the capacitordielectric layer. The capacitor dielectric layer may include a baselayer on the lower electrode and including a first dielectric material,and a dielectric particle layer in at least a portion of the base layer.The dielectric particle layer may at least partially continuously extendalong a thickness direction of the capacitor dielectric layer andincluding a second dielectric material different from the firstdielectric material.

According to example embodiments of the inventive concepts, a method ofmanufacturing a semiconductor device may include forming a firstelectrode on a substrate, forming a base layer on the first electrodeusing a first dielectric material, forming a dielectric particle layerin at least a portion of the base layer using a second dielectricmaterial to at least partially extend along a grain boundary of the baselayer in a thickness direction of the base layer, and forming a secondelectrode on the base layer and the dielectric particle layer.

According to example embodiments of the inventive concepts, asemiconductor device may include a first electrode, a second electrode,and a capacitor dielectric layer. The capacitor dielectric layer mayinclude a base layer extending between the first and second electrodesto define a thickness thereof, and a dielectric particle layer extendingwithin the base layer along the thickness of the base layer. The baselayer may include a dielectric material that is different from that ofthe dielectric particle layer. The dielectric particle layer may extendalong grain boundaries defined between adjacent crystal grains of thebase layer. The adjacent crystal grains of the base layer may define afirst surface roughness, and the capacitor dielectric layer may have asecond surface roughness that is less than the first surface roughness.

BRIEF DESCRIPTION OF THE DRAWINGS

Example embodiments will be more clearly understood from the followingdetailed description taken in conjunction with the accompanyingdrawings.

FIG. 1 is a cross-sectional view illustrating a capacitor structureaccording to example embodiments of the inventive concepts.

FIG. 2 is a cross-sectional view illustrating a capacitor structureaccording to example embodiments of the inventive concepts.

FIG. 3 is a cross-sectional view illustrating a capacitor structureaccording to example embodiments of the inventive concepts;

FIG. 4 is a cross-sectional view illustrating a capacitor structureaccording to example embodiments of the inventive concepts.

FIG. 5 is a cross-sectional view illustrating a capacitor structureaccording to example embodiments of the inventive concepts.

FIG. 6A is a schematic lay-out diagram illustrating a semiconductordevice according to example embodiments of the inventive concepts.

FIG. 6B is a cross-sectional view taken along line B-B′ of FIG. 6A.

FIG. 7 is a cross-sectional view illustrating a semiconductor deviceaccording to example embodiments of the inventive concepts.

FIG. 8 is a flow-chart diagram illustrating a method of manufacturing acapacitor structure according to example embodiments of the inventiveconcepts.

FIGS. 9A and 9B are cross-sectional views illustrating operations orstages of a method of manufacturing a capacitor structure according toexample embodiments of the inventive concepts.

FIG. 10 is a flow-chart diagram illustrating a method of manufacturing acapacitor structure according to example embodiments of the inventiveconcepts.

FIGS. 11A and 11B are cross-sectional views illustrating operations orstages of a method of manufacturing a capacitor structure according toexample embodiments of the inventive concepts.

FIG. 12 is a flow-chart diagram illustrating a method of manufacturing acapacitor structure according to example embodiments of the inventiveconcepts.

FIGS. 13A to 13C are cross-sectional views illustrating operations orstages of a method of manufacturing a capacitor structure according toexample embodiments of the inventive concepts.

FIG. 14 is a flow-chart diagram illustrating a method of manufacturing acapacitor structure according to example embodiments of the inventiveconcepts.

FIGS. 15A and 15B are cross-sectional views illustrating operations orstages of a method of manufacturing a capacitor structure according toexample embodiments of the inventive concepts.

FIG. 16 is a flow-chart diagram illustrating a method of manufacturing acapacitor structure according to example embodiments of the inventiveconcepts.

FIGS. 17A and 17B are cross-sectional views illustrating operations orstages of a method of manufacturing a capacitor structure according toexample embodiments of the inventive concepts.

FIGS. 18A to 18H are cross-sectional views illustrating operations orstages of a method of manufacturing a semiconductor device according toexample embodiments of the inventive concepts.

FIGS. 19A to 19E are cross-sectional views illustrating operations orstages of a method of manufacturing a semiconductor device according toexample embodiments of the inventive concepts.

FIG. 20A is a schematic view and an equivalent circuit diagramillustrating a capacitor structure according to example embodiments ofthe inventive concepts.

FIG. 20B is a schematic view and an equivalent circuit diagramillustrating a capacitor structure according to a comparative example.

FIG. 21 is a graph illustrating a relationship between a breakdownvoltage and an equivalent oxide thickness of a capacitor structureaccording to example embodiments of the inventive concepts.

DETAILED DESCRIPTION OF EMBODIMENTS

Various example embodiments will now be described more fully withreference to the accompanying drawings in which some example embodimentsare shown. However, the inventive concepts may be embodied in manyalternate forms and should not be construed as limited to only exampleembodiments set forth herein.

FIG. 1 is a cross-sectional view illustrating a capacitor structure 10according to example embodiments of the inventive concepts.

Referring to FIG. 1, the capacitor structure 10 may include a firstelectrode 22, a second electrode 24 and a capacitor dielectric layer 30interposed between the first electrode 22 and the second electrode 24.

In some embodiments, the first electrode 22 may include one or more ofdoped polysilicon, metal such as ruthenium (Ru), iridium (Ir), titanium(Ti), tantalum (Ta), tungsten (W), conductive metal nitride such astitanium nitride (TiN), tantalum nitride (TaN), tungsten nitride (WN),and conductive metal oxide such as iridium oxide, etc. In otherembodiments, the first electrode 22 may be a substrate doped withimpurities, for example, a substrate doped with p-type impurities orn-type impurities.

In some embodiments, the second electrode 24 may include one or more ofa doped polysilicon, a metal such as ruthenium (Ru), iridium (Ir),titanium (Ti), tantalum (Ta), tungsten (W), a conductive metal nitridesuch as titanium nitride (TiN), tantalum nitride (TaN), tungsten nitride(WN), and a conductive metal oxide such as iridium oxide, etc.

In some embodiments, the first electrode 22 may correspond to a lowerelectrode of the capacitor 10, and the second electrode 24 maycorrespond to an upper electrode of the capacitor 10. In otherembodiments, according to a shape of the capacitor 10, the firstelectrode 22 may correspond to the upper electrode of the capacitor 10,and the second electrode 24 may correspond to the lower electrode of thecapacitor 10. In some embodiments, the first electrode 22 may be achannel region of a transistor.

The capacitor dielectric layer 30 may have a first thickness T1 and maybe conformally formed on the first electrode 22. Here, a directionparallel to a top surface of the first electrode 22 is referred to as afirst direction D1, and a direction vertical or perpendicular to the topsurface of the first electrode 22 is referred to as a second directionD2 (e.g. a thickness direction of the capacitor dielectric layer 30).The capacitor dielectric layer 30 may have the first thickness T1 alongthe second direction D2, and the first thickness T1 may range from about10 Å to about 200 Å, preferably about 10 Å to about 100 Å, morepreferably about 20 Å to about 80 Å, even more preferably about 30 Å toabout 60 Å.

The capacitor dielectric layer 30 may include a base layer 42 and adielectric particle layer 44. The capacitor dielectric layer 30 mayinclude a plurality of the dielectric particle layers 44.

The base layer 42 may be arranged in the first direction D1. The baselayer 42 may include a first dielectric material, for example, a high-kdielectric material such as a metal oxide. The first dielectric materialmay have a higher dielectric constant (e.g., a dielectric constant of 4to 40) than that of silicon oxide (SiO₂). In some embodiments, the firstdielectric material may include zirconium oxide (ZrO₂), hafnium oxide(HfO₂) , zirconium silicon oxide (ZrSiO_(x)), hafnium silicon oxide(HfSiO_(x)), zirconium hafnium silicon oxide (ZrHfSiO_(x)), aluminumoxide (Al₂O₃), or combinations thereof, but not limited thereto.

As shown in FIG. 1, the base layer 42 may include a plurality of crystalgrains GR extending in a thickness direction (e.g., the second directionD2) of the capacitor dielectric layer 30. Grain boundaries GB may beformed between the crystal grains GR. The grain boundary GB may be aboundary or an interface between the adjacent crystal grains GR. Thegrain boundary GB may be vertically arranged or inclined at a certainangle relative to the top surface of the first electrode 22. Forexample, the grain boundary GB may mainly extend in the second directionD2 or be inclined at a certain angle (e.g., at an angle of less than 20degrees) relative to the second direction D2, but not limited thereto.In a process of forming the base layer 42, since the crystal grains GRof the base layer 42 may each be mainly grown along the second directionD2, the grain boundary GB formed at an interface between the adjacentcrystal grains GR may extend along substantially the second direction D2or be inclined relative to the second direction D2.

The dielectric particle layer 44 may be disposed at or extending alongat least a portion of the grain boundary GB. The dielectric particlelayer 44 may be disposed in at least a portion of the base layer 42. Thedielectric particle layer 44 may include a second dielectric materialdifferent from the first dielectric material. The second dielectricmaterial may have a higher band gap energy (Eg), such as silicon oxideor metal oxide, and a smaller dielectric constant than the firstdielectric material. For example, the second dielectric material mayhave a dielectric constant of about 3.9 to about 40 and a band gapenergy (Eg) of about 4 to about 10 Ev. In some embodiments, the seconddielectric material include aluminum oxide (AL₂O₃), Beryllium oxide(BeO), boron oxide (B₂O₃), silicon oxide (SiO₂), scandium oxide (Sc₂O₃),yttrium oxide (Y2O3), lanthanum oxide (La2O3), zirconium hafnium siliconoxide (ZrHfSiOx), aluminum nitride (AlN), boron nitride (BN), siliconnitride (Si₃N₄) or combinations thereof, but not limited thereto.

As shown in FIG. 1, the dielectric particle layer 44 may includedielectric nanoparticles dispersed at or along the grain boundary of thebase layer 42. Here, the dielectric particle layer 44 may be referred toas a set of the dielectric nanoparticles. That is, the dielectricmaterial particles may contact the grain boundary GB of the base layer44 and may be collectively disposed adjacent to the grain boundary GB.The dielectric nanoparticles may be disposed on a top surface of thebase layer 42. Some of the dielectric nanoparticles of the dielectricparticle layer 44 may be in contact with each other and may agglomerateeach other. Some of the dielectric nanoparticles may randomly bedispersed. The dielectric particle layer 44 may at least partiallycontinuously extend in at least a portion of the base layer 42. Aportion of the dielectric particle layer 44 may extend in the thicknessdirection (i.e., the second direction D2) of the capacitor dielectriclayer 30. The dielectric nanoparticles have a diameter of about 1 Å to10 Å and may have a spherical shape, a hemispherical shape, anelliptical shape or a dot-shape, but embodiments of the inventiveconcepts are not limited thereto.

In some embodiments, a mass ratio of the base layer 42 to the dielectricparticle layer 44 in the capacitor dielectric layer 30 may be in a rangeof about 70:30 to about 95:5. For example, the base layer 42 may occupya considerable amount (e.g., about 70% to about 95%) of a total mass ofthe capacitor dielectric layer 30. Additionally, a contact area betweenthe first electrode 22 and the base layer 42 or between the secondelectrode 24 and the base layer 42 may be in a range of about 70% toabout 95% of a contact area between the first electrode 22 and thecapacitor dielectric layer 30 or between the second electrode 24 and thecapacitor dielectric layer 30, but embodiments of the inventive conceptsare not limited thereto.

Some of the plurality crystal grains GR of the base layer 42 may contactthe dielectric particle layer 44 to form an interface, and the interfacebetween the some of the plurality of crystal grains GR and thedielectric particle layer 44 may extend in the second direction D2(e.g., the thickness direction of the capacitor dielectric layer 30)from the top surface of the base layer 42 to a bottom surface thereof.Accordingly, the dielectric particle layer 44 may be interposed betweenthe adjacent crystal grains GR of the base layer 42 and may be disposedbetween a first and second electrodes 22 and 24, thereby forming asub-capacitor domain D_DP (refer to 20A). As a result, a sub-capacitordomain D_BL (refer to 20A) formed by the plurality of crystal grains GRof the base layer 42 and the sub-capacitor domain D_DP formed by thedielectric particle layer 44 may be connected in parallel, and thus thecapacitor structure 10 may have a high capacitance. This will bedescribed in detail later with reference to FIGS. 20A and 20B.

In some embodiments, the capacitor dielectric layer 30 may have a flator substantially planar top surface profile and a low surface roughness.The capacitor dielectric layer 30 may have a surface roughness of about0.3 nm or less, preferably about 0.2 nm or less. The base layer 42 mayhave the plurality of crystal grains GR that extend in the seconddirection D2, and the dielectric particle layer 44 may be disposed in aspace between the crystal grains GR at the grain boundary GB and mayinclude the dielectric nanoparticles having the spherical shape or theelliptical shape such that the capacitor dielectric layer 30 may have aflat or substantially planar top surface profile.

In general, in embodiments in which the top surface profile of thecapacitor dielectric layer 30 is not flat or the surface roughnessthereof is high, a void may be formed between the first electrode 22 andthe capacitor dielectric layer 30 or between the second electrode 24 andthe capacitor dielectric layer 30. Due to a thermal or electrical stressgenerated during the process of forming the capacitor structure 10 orthe following process, the void may be enlarged or defects in thecapacitor dielectric layer 30 may be concentrated into the void. Thus,the void may be a leakage current path in the capacitor structure 10,and/or a breakdown of the capacitor dielectric layer 30 or a shortcircuit between the first electrode 22 and the second electrode 24 maygenerated through the void.

However, although the base layer 42 includes a relatively high surfaceroughness, since the dielectric particle layer 44 is disposed betweenthe crystal grains GR of the base layer 42, the entire top surfaceprofile of the capacitor dielectric layer 30 may be improved.Accordingly, the leakage current of the capacitor structure 10 may bereduced and the breakdown or the short circuit of the capacitorstructure 10 may be reduced or prevented from occurring.

A first interface layer 52 may be selectively disposed between the firstelectrode 22 and the capacitor dielectric layer 30, and a secondinterface layer 54 may be disposed between the second electrode 24 andthe capacitor dielectric layer 30. For example, the first and secondinterface layers 52 and 54 may act as a barrier layer to reduce orprevent impurities from diffusing and/or moving between the firstelectrode 22 and the capacitor dielectric layer 30 or between the secondelectrode 24 and the capacitor dielectric layer 30. For example, thefirst and second interface layers may reduce or prevent some of nitrogenatoms contained in the first and second electrodes 22 and 24 frompenetrating into the capacitor dielectric layer 30 and/or may reduce orprevent oxygen atoms contained in the capacitor dielectric layer 30 10from diffusing into the first and second electrodes 22 and 24 whilemanufacturing the capacitor structure 10.

In some embodiments, the first and second interface layers 52 and 54 mayinclude an electrically conductive transition metal oxide, such astitanium oxide (TiO_(x), 0<x<2), titanium aluminum oxide (TiAlO_(x)),manganese oxide (MnO_(x), 0<x<2), or TiON, but not limited thereto. Thefirst and second interface layers 52 and 54 may be thinly formed not toact as a capacitor dielectric layer of the capacitor structure. Forexample, the first and second interface layers 52 and 54 may have athickness of about 1 Å to 10 Å in the second direction D2, but notlimited thereto.

In some embodiments, the first and second interface layers 52 and 54 maybe omitted, and thus the capacitor dielectric layer 30 may be formed todirectly contact the first and second electrodes 22 and 24.

In some embodiments, the first interface layer 52 may be omitted and thesecond interface layer 54 may be formed between the second electrode 24and the capacitor dielectric layer 30.

In some embodiments, the second interface layer 54 may be omitted andthe first interface layer 52 may be formed between the first electrode22 and the capacitor dielectric layer 30.

Hereinafter, with reference to FIGS. 20A and 20B along with FIG. 1, acapacitance model of the capacitor dielectric layer 30 is described.

FIG. 20A shows a schematic cross-sectional view of a capacitor structureEX-10 and an equivalent circuit diagram thereof according to exampleembodiments of the inventive concepts as described with reference toFIG. 1.

For example, as shown in FIG. 20A, the dielectric particle layer 44 (DP)may have a predetermined width and may extend in the second direction D2(e.g., a vertical direction to a top surface of a lower electrode LE).In this case, a portion of the dielectric particle layer 44 (DP)disposed between the lower electrode LE and an upper electrode UE mayact as a capacitor dielectric layer of the capacitor structure EX-10.Accordingly, the capacitor structure EX-10 may represent a capacitanceof the dielectric particle layer 44 (DP), as well as a capacitance ofthe base layer 42 (BL).

Specifically, the crystal grains GR of the base layer 42 (BL) may formthe first sub-domain D_BL between the upper and lower electrodes UE andLE, and the dielectric particle layer 44 (DP) may form the secondsub-domain D_DP between the upper and lower electrodes UE and LE.Further, a contact area A_DP of the dielectric particle layer 44 (DP)contacting the lower electrode LE or upper electrode UE and a contactarea A_BL of the base layer 42 (BL) contacting the lower electrode LE orupper electrode UE may be respectively obtained.

As shown in the equivalent circuit diagram at a bottom of FIG. 20A, thefirst sub-domain D_BL and the second sub-domain D_DP may be connected inparallel with each other, and thus a total capacitance C(total) of thecapacitor structure EX-10 may be equal to a sum of a first capacitanceC1(D_BL) obtained from the first sub-domain D_BL and a secondcapacitance C2(D_DP) obtained from the second sub-domain D_DP (i.e., itcan be expressed by the following equation: C(total) =C1(D_BL)+C2(D_DP).

FIG. 20B shows a schematic cross-sectional view of a capacitor structureCO-10 and an equivalent circuit diagram thereof according to acomparative example.

Referring to FIG. 20B, the capacitor structure CO-10 according to thecomparative example may include a capacitor dielectric layer CO-30between a lower electrode LE and an upper electrode UE, and thecapacitor dielectric layer CO-30 may include a first base layer BL1, afirst dielectric layer DP1, a second base layer BL2 and a seconddielectric layer DP2 that are sequentially stacked on the lowerelectrode LE. Here, each layer of the capacitor dielectric layer CO-30may be conformally arranged with a predetermined thickness and mayextend in the first direction D1.

As shown in the equivalent circuit diagram at the bottom of FIG. 20B, inthe capacitor structure CO-10 according to the comparative example, thefirst base layer BL1, the first dielectric layer DP1, the second baselayer BL2 and the second dielectric layer DP2 may be respectivelycorrespond to a first capacitor, a second capacitor, a third capacitorand a fourth capacitor that are connected in series with each other.Accordingly, a total capacitance of the capacitor structure CO-10 may bedetermined from the following Equation 1:1/C(total)=1/C1(BL1)+1/C2(DP1)+1/C3(BL2)+1/C4(DP2)  Equation 1

According to the equation 1, the total capacitance C(total) of thecapacitor structure according to the comparative example may bedetermined based on a dielectric constant and a thickness of each layerof the capacitor dielectric layer CO-30. Meanwhile, a total thicknessT1-CO of the capacitor dielectric layer CO-30 may be smaller as thesemiconductor device is scaled down, and thus, the thickness of eachlayer of the capacitor dielectric layer CO-30 may also be reduced.

In general, when the first and second base layers BL1 and BL2 are thin,crystallinity of the first and second base layers BL1 and BL2 may bereduced, and/or the first and second base layers BL1 and BL2 may have anamorphous structure. In this case, a dielectric constant of the firstand second base layers BL1 and BL2 may be decreased. For example, whenthe second base layer BL2 is formed to a thickness T-BL2 of less than apredetermined critical thickness in order to reduce the total thicknessT1-CO of the capacitor dielectric layer CO-30, the second base layer BL2having the amorphous structure may be formed. For example, inembodiments in which the first and second base layers BL1 and BL2include zirconium oxide (ZrO₂), a dielectric constant of an amorphouszirconium oxide may be about 30% smaller than a dielectric constant of acrystal zirconium oxide. Accordingly, the capacitance C(total) of thecapacitor structure CO-30 may be further reduced depending on areduction of the total thickness T1-CO of the capacitor structure CO-30.

However, the capacitor structure EX-10 according to the exampleembodiment of the inventive concepts, since the base layer 42(BL) isformed to a thickness equal to the entirety of the total thickness T1-EXof the capacitor dielectric layer EX-30, crystallinity of the base layer42(BL) may not be reduced and the base layer 42(BL) may not also have anamorphous structure. Accordingly, when the capacitor dielectric layerEX-30 has a thickness greater than the predetermined critical thicknessalthough the thickness T1-EX of the capacitor dielectric layer EX-30 isdecreased, the base layer 42 (BL) may be formed in a crystal structure,and thus the base layer 42(BL) may have a high dielectric constant incomparison with the base layer 42(BL) of the amorphous structure. Inother words, although the capacitor structure EX-10 is thin, thecapacitor structure EX-10 may have a high capacitance. In embodiments inwhich the capacitor structure EX-10 includes the capacitor dielectriclayer EX-30 that has a thin thickness T1-EX of less than 100 Å and ofwhich the base layer 42(BL) is formed using zirconium oxide and thedielectric particle layer 44 (DP) is formed using aluminum oxide, thecapacitance of the capacitor dielectric layer EX-30 may be about 20%higher than that of the capacitor dielectric layer CO-30 according tothe comparative example having the same thickness T1-CO as the capacitordielectric layer EX-30. This result can be confirmed through theexperimental result of FIG. 21.

FIG. 21 is a graph illustrating a relationship between a breakdownvoltage (V) and an equivalent oxide thickness (Å) of the capacitorstructure EX-10 according to the example embodiment. In addition, inFIG. 21, a relationship between a breakdown voltage (V) and anequivalent oxide thickness (Å) of the capacitor structure CO-10according to the comparative example are illustrated.

Referring to FIG. 21, it can be confirmed that the capacitor structureEX-10 according to the example embodiment has a lower equivalent oxidethickness and a higher breakdown characteristic, as compared to thecapacitor structure CP-10 according to the comparative example.

Referring again to FIG. 1, although the capacitor structure 10 accordingto the example embodiment includes the capacitor dielectric layer 30having a thin first thickness T1, the capacitor structure 10 may have ahigh capacitance, and the leakage current or the short circuit betweenthe first and second electrodes 22 and 24 through the capacitordielectric layer 30 may be reduced or prevented from occurring.

FIG. 2 is a cross-sectional view illustrating a capacitor structure 10Aaccording to example embodiments of the inventive concepts. In FIG. 2,the same reference numerals denote the same elements as in FIG. 1.

Referring to FIG. 2, the capacitor structure 10A may include a capacitordielectric layer 30A including a base layer 42 and a dielectric particlelayer 44A. The dielectric particle layer 44A may have a first width W1in the first direction D1 and may have a pillar shaped cross-sectioncontinuously extending in the second direction D2 over the entirethickness of the capacitor dielectric layer 30A from a top surface ofthe capacitor dielectric layer 30A to a bottom surface thereof.

In the capacitor structure 10A, the dielectric particle layer 44A may bedisposed to continuously fill a space between crystal grains GR of thebase layer 42. For example, when the dielectric particle layer 44Aincludes a material having an improved gap-filling property, thedielectric particle layer 44A may be formed to have a pillar shapedcross-section continuously extending over the entire thickness of thecapacitor dielectric layer 30A.

The dielectric particle layer 44A may have the first width W1 that issubstantially uniform, but embodiments of the inventive concepts are notlimited thereto. The dielectric particle layer 44A may vertically extendrelative to a top surface of a first electrode 22 as show in FIG. 2, butembodiments of the inventive concepts are not limited thereto. In someembodiments, the dielectric particle layer 44A, and the crystal grain GRor a grain boundary GB of the base line 30A may extend while inclined ata certain angle relative to the top surface of a first electrode 22.

A dielectric capping layer 60 may be disposed on the base layer 42 andthe dielectric particle layer 44A. The dielectric capping layer 60 mayinclude a third dielectric material. The third dielectric material maybe a dielectric material having a high band gap energy (Eg), such assilicon oxide, metal oxide, and a lower dielectric constant than thesecond dielectric material. For example, the third dielectric materialmay have a band gap energy (Eg) of about 5 to about 10 Ev and adielectric constant of about 3.9 to about 40. In some embodiments, thethird dielectric material may include aluminum oxide (Al₂O₃), berylliumoxide (BeO), boron oxide (B₂O₃), silicon oxide (SiO₂), scandium oxide(Sc₂O₃), yttrium oxide (Y₂O₃), lanthanum oxide (La₂O₃), zirconiumhafnium silicon oxide (ZrHfSiOx), aluminum nitride (AlN), boron nitride(BN), silicon nitride (Si₃N₄) or combinations thereof, but not limitedthereto.

In some embodiments, the dielectric capping layer 60 may include thesame material as the dielectric particle layer 44A. For example, whenthe dielectric particle layer 44A includes aluminum oxide (Al₂O₃), thedielectric capping layer 60 may include aluminum oxide (Al₂O₃). Forexample, when the dielectric particle layer 44A includes boron oxide(B₂O₃), the dielectric capping layer 60 may include boron oxide (B₂O₃).In other embodiments, the dielectric capping layer 60 may include adifferent material from the dielectric particle layer 44A. For example,when the dielectric particle layer 44A includes aluminum oxide (Al₂O₃),the dielectric capping layer 60 may include aluminum nitride (AlN). Forexample, when the dielectric particle layer 44A includes boron oxide(B₂O₃), the dielectric capping layer 60 may include boron nitride (BN),but not limited thereto.

The dielectric capping layer 60 may act as a protection layer to reduceor prevent moisture or humidity from penetrating into the capacitordielectric layer 30A through the dielectric particle layer 44A orthrough an interface between the dielectric particle layer 44A and thebase layer 42. Additionally, the dielectric capping layer 60 may act asa leveling layer to reduce a surface roughness of the capacitordielectric layer 30A.

FIG. 3 is a cross-sectional view illustrating a capacitor structure 10Baccording to example embodiments of the inventive concepts. In FIG. 3,the same reference numerals denote the same elements as in FIGS. 1 and2.

Referring to FIG. 3, a dielectric particle layer 44B may continuouslyextend in the second direction D2 over an entire thickness of acapacitor dielectric layer 30B from a top surface of the capacitordielectric layer 30B to a bottom surface thereof. In the dielectricparticle layer 44B, a width W2 of one end thereof facing a firstelectrode 22 may be smaller than a width W3 of another end thereoffacing a second electrode 24. Thus, the lower width W2 of the dielectricparticle layer 44B may be smaller than the upper width W3 thereof alongthe second direction D2 from a top surface of the first electrode 22.When crystal grains GR of a base layer 42 have a high surface roughness,a relatively large space between the crystal grains GR may be formed ata top of the base layer 42 as compared to at a bottom of the base layer42. The dielectric particle layer 44B may be formed to fill the spacebetween the crystal grains GR, and thus may have a pillar shapedcross-section that has the upper width W3 greater than the lower widthW2, but embodiments of the inventive concepts are not limited thereto.In some embodiments, the relatively large space between the crystalgrains GR of the base layer 42 may be formed at the bottom of the baselayer 42 as compared to at the top of the base layer 42, and thedielectric particle layer 44B may be formed to fill the space betweenthe crystal grains GR such that the lower width of the dielectricparticle layer 44B is greater than the upper width thereof.

FIG. 4 is a cross-sectional view illustrating a capacitor structure 10Caccording to example embodiments of the inventive concepts. In FIG. 4,the same reference numerals denote the same elements as in FIGS. 1 to 3.

Referring to FIG. 4, the capacitor structure 10C may include a capacitordielectric layer 30C including a first dielectric layer 32 and a seconddielectric layer 34 that are sequentially stacked on a first electrode22. The first dielectric layer 32 may include a first base layer 42 anda first dielectric particle layer 44 disposed between crystal grains GRof the first base layer 42, and the second dielectric layer 34 mayinclude a second base layer 46 and a second dielectric particle layer 48disposed between crystal grains GR of the second base layer 46. Thefirst and second base layers 42 and 46 and the first and seconddielectric particle layers 44 and 48 may respectively have the samefeatures as the base layer 42 and the dielectric particle layer 44 asdescribed with reference to FIG. 1.

The first dielectric layer 32 may have a first thickness T1 along asecond direction D2 (e.g. a thickness direction of a capacitordielectric layer 30C). The second dielectric layer 34 may have a secondthickness T2 along the second direction D2. The first thickness T1 maybe equal to or different from the second thickness T2.

In some embodiments, in the capacitor dielectric layer 30C, the firstdielectric layer 32 including the first base layer 42 and the firstdielectric layer 44 may have a structure including three or more layersstacked in the second direction.

In an example method for forming the capacitor dielectric layer 30C,after forming the first base layer 42 on the first electrode 22, thefirst dielectric particle layer 44 may be formed at a grain boundary GBof the first base layer 42, and the second base layer 46 may be formedon the first base layer 42 and the first dielectric particle layer 44.In this case, the first dielectric layer 32 may have a flat orsubstantially planar top surface profile and a low surface roughness.Thus, when forming the second base layer 46 on the first dielectriclayer 32 having the flat or substantially planar top surface profile,the second base layer 46 may be formed to have an improvedcrystallinity.

FIG. 5 is a cross-sectional view illustrating a capacitor structure 10Daccording to example embodiments of the inventive concepts. In FIG. 5,the same reference numerals denote the same elements as in FIGS. 1 to 4.

Referring to FIG. 5, the capacitor structure 10D may include a capacitorinsulating layer 30D including a first dielectric layer 32 and a seconddielectric layer 34 that are sequentially stacked on a first electrode22. The first dielectric layer 32 may include a first base layer 42 anda first dielectric particle layer 44 disposed at only a grain boundaryof an upper portion of the first base layer 42. In other words, thefirst dielectric particle layer 44 may be formed with a predeterminedheight toward a bottom surface of the first dielectric layer 32 from atop surface of the first dielectric layer 32 and may not be formed atthe grain boundary of a lower portion of the base layer 42. That is, thelower portion of the base layer 42 may be free of the first dielectricparticle layer 44.

In a process for forming the capacitor dielectric layer 30D, afterforming the first base layer 42 on the first electrode 22, a second baselayer 46 may be formed on the first base layer 42. Next, a seconddielectric particle layer 48 including dielectric nanoparticles may beformed at a grain boundary GB of the second base layer 46. Thedielectric nanoparticles may diffuse or move along a space betweencrystal grains GR of the second base layer 46, and thus some of thedielectric nanoparticles may be disposed at the grain boundary of theupper portion of the first base layer 42 to form the first dielectricparticle layer 44.

FIG. 6A is a schematic lay-out diagram illustrating a semiconductordevice 100 according to example embodiments of the inventive concepts.FIG. 6B is a cross-sectional view taken along line B-B′ of FIG. 6A. InFIGS. 6A and 6B, the same reference numerals denote the same elements asin FIGS. 1 to 5.

Referring to FIGS. 6A and 6B, the substrate 102 may include an activeregion 106 defined by an isolation layer 104. A plurality of activeregions 106 may be formed in the substrate 102.

The substrate 102 may include silicon (Si), e.g., crystalline silicon,polycrystalline silicon, or amorphous silicon. In some embodiments, thesubstrate 102 may include a semiconductor material, such as germanium(Ge), silicon germanium (SiGe), silicon carbide (SiC), gallium arsenide(GaAs), indium arsenide (InAs), or indium phosphide (InP). The substrate102 may include a conductive region, e.g., a well doped with impuritiesor a structure doped with impurities.

The isolation layer 104 may have a shallow trench isolation (STI)structure. The isolation layer 104 may include an insulating materialfilling an isolation trench 104T formed in the substrate 102. Theinsulating material may include fluoride silicate glass (FSG), undopedsilicate glass (USG), boro-phospho-silicate glass (BPSG),phospho-silicate glass (PSG), flowable oxide (FOX), plasma enhancedtetra-ethyl-ortho-silicate (PE-TEOS), tonen silazene (TOSZ) orcombinations thereof, but not limited thereto.

The active region 106 may have a long island shape that has a short axisand a long axis. The long axis of the active region 106 may be parallelto a D3 direction parallel to a top surface of the substrate 102. Insome embodiments, the active region 106 may have a first conductivitytype. The first conductivity type may be p-type or n-type.

The substrate 102 may include a trench 108 extending along an Xdirection parallel to the top surface of the substrate and crossing theD3 direction at a certain angle. The trench 108 may traverse the activeregion 106 and may be formed to a predetermined depth. A portion of thetrench 108 may extend into the isolation layer 104. The portion of thetrench 108 in the isolation layer 104 may have a bottom surfacepositioned at a lower level than other portion of the trench 108 in theactive region 106.

A first source/drain region 109A and a second source/drain region 109Bmay be disposed in an upper portion of the active region 106 at oppositesides of the trench 108. The first and second source/drain regions 109Aand 109B may be impurity regions doped with impurities of a secondconductivity type different from the first conductivity type. The secondconductivity type may be n-type or p-type.

A gate structure 120 may be formed in the trench 108. The gate structure120 may include a gate insulating layer 122, a gate electrode 124 and agate capping layer 126 that are sequentially formed on an inner surfaceof the trench 108.

The gate insulating layer 122 may be conformally formed to apredetermined thickness on the inner surface of the trench 108. The gateinsulating layer 122 may include one or more of silicon oxide, siliconoxynitride, silicon nitride and a high-k dielectric material having ahigher dielectric constant than silicon oxide. The high-k dielectricmaterial may include metal oxide or metal oxynitride, such as hafniumoxide, hafnium oxynitride, hafnium silicon oxide, but not limitedthereto. In some embodiments, when the gate insulating layer 122includes silicon oxide, the gate insulating layer 122 may be formed onan exposed surface of the substrate 102 by a thermal oxidation process.In other embodiments, the gate insulating layer 122 may be formed by alow pressure chemical vapor deposition (LPCVD) process, a plasma enhanceCVD (PECVD) process, an ultra-high vacuum CVD (UHV-CVD) process, or anatomic layer deposition (ALD) process.

The gate electrode 124 may be formed on the gate insulating layer 122 tofill the trench 108 to a predetermined height from the bottom surface oftrench 108. The gate electrode 124 may include a work functionadjustment layer on the gate insulating layer 122 and a buried metallayer, on the work function adjustment layer, filling a lower portion ofthe trench 108. The work function adjustment layer include metal, metaloxide or metal carbide, such as TiN, TiAlN, TiAlC, TiAlCN, TiSiCN, Ta,TaN, TaAlN, TaAlCN, TaSiCN, etc. The buried metal layer may include oneor more of W, WN, TiN and TaN.

The gate capping layer 126 may be formed on the gate electrode layer 124to fill a remaining portion of the trench 108. The gate capping layer126 may include one or more of silicon oxide, silicon nitride andsilicon oxynitride.

The gate electrode 124 may have a top surface positioned at a higherlevel than bottom surfaces of the first and second source/drain regions109A and 109B. In some embodiments, the bottom surface of one of thefirst and second source/drain regions 109A and 109B may be positioned ata lower level than the bottom surface of the other of the first andsecond source/drain regions 109A and 109B such that the first and secondsource/drain regions 109A and 109B have different heights. In this case,for example, the top surface of the gate electrode 124 may be positionedat a lower level than the bottom surface of the first source/drainregion 109A and at a higher level than the bottom surface of the secondsource/drain region 109B. In some embodiments, the gate electrode 124may have a top surface positioned at a lower level than bottom surfacesof the first and second source/drain regions 109A and 109B.

A bit line structure 130 may be formed on the first source/drain region109A to extend along a Y direction parallel to the top surface of thesubstrate 102 and vertical or perpendicular to the X direction. The bitline structure 130 may include a bit line contact 132, a bit line 134and a bit line capping layer 136 that are sequentially stacked on thesubstrate 102. For example, the bit line contact 132 may includepolysilicon, and the bit line 134 may include metal. The bit linecapping layer 136 may include an insulating material such as siliconnitride or silicon oxynitride.

A bit line intermediate layer may further be interposed between the bitline contact 132 and the bite line 134. The bit line intermediate layermay include metal silicide such as tungsten silicide or metal nitridesuch as tungsten nitride. A bit line spacer may further be formed onsidewalls of the bit line structure 130. The bit line spacer may includea single- or multi-layer structure formed of an insulating material suchas silicon oxide, silicon oxynitride or silicon nitride. The bit linespacer may further include an air space.

A first insulating interlayer 142 may be formed on the substrate 102.The bit line contact 132 may penetrate the first insulating interlayer142 to be connected to the first source/drain region 109A. The bit line134 and the bit line capping layer 136 may be disposed on the firstinsulating interlayer 142. A second insulating interlayer 144 may bedisposed on the first insulating interlayer 142 to extend on or coverthe bit line 134 and the bit line capping layer 136.

A contact structure 146 may be formed on the second source/drain region109B. The first and second insulating interlayer 142 and 144 may extendon or cover sidewalls of the contact structure 146. In some embodiments,the contact structure 146 may include a lower contact pattern, a metalsilicide layer and upper contact pattern that are sequentially stackedon the substrate 102 and a barrier layer surrounding sidewalls and abottom surface of the upper contact pattern. In some embodiments, thelower contact pattern may include polysilicon, and the upper contactpattern may include metal. The barrier layer may include metal nitride.

A capacitor structure 160 may be formed on the second insulatinginterlayer 144. The capacitor structure 160 may include a lowerelectrode 162 electrically connected to the contact structure 146, acapacitor dielectric layer 164 on the lower electrode 162 and an upperelectrode 166 on the capacitor dielectric layer 164. An etch stop layer150 including an opening 150T may be formed on the second insulatinginterlayer 144. A lower portion of the lower electrode 162 may bedisposed in the opening 150T of the etch stop layer 150.

The lower electrode 162 may be formed on the contact structure 146 in acylindrical shape having a closed bottom or a cup shape, and thecapacitor dielectric layer 164 may be conformally formed on the lowerelectrode 162. The capacitor dielectric layer 164 may include a baselayer 164_1 and a dielectric particle layer 164_2 disposed between thecrystal grains of the base layer 164_1. The base layer 164_1 and thedielectric particle layer 164_2 may have the same features as the baselayer 42 and the dielectric particle layer 44 of FIG. 1. Accordingly,further details of the base layer 164_1 and the dielectric particlelayer 164_2 may refer to the detailed descriptions of the base layer 44and the dielectric particle layer 44 made with reference to FIG. 1.Meanwhile, the capacitor dielectric layer 164 may have features similarto or the same as the capacitor dielectric layers 30A, 30B, 30C and/or30D as described with reference to FIGS. 2 to 5.

A first interface layer 172 and the second interface layer 174 may beformed between the capacitor dielectric layer 164 and the lowerelectrode 162 and between the capacitor dielectric layer 164 and theupper electrode 166, respectively. The first and second interface layers172 and 174 may have the same or similar features as the first andsecond interface layers 52 and 54 as described with reference to FIG. 1.

In some embodiments, in the semiconductor device 100 according to theexample embodiment, although a thickness of the capacitor dielectriclayer 164 is small, the capacitor structure may have a high capacitanceand a leakage current or a short circuit between the lower and secondelectrodes 162 and 164 through the capacitor dielectric layer 164 may bereduced or prevented from occurring.

FIG. 7 is a cross-sectional view illustrating a semiconductor device100A according to example embodiments of the inventive concepts. FIG. 7is the cross-sectional view corresponding to a cross-section taken alongB-B′ of FIG. 6A. In FIG. 7, the same reference numerals denote the sameelements as in FIGS. 1 to 6B.

Referring to FIG. 7, a capacitor structure 160A may have a pillar shapedlower electrode layer 162A. A supporting member 180 may be disposed on aportion of a sidewall of the lower electrode 162A to reduce or preventcollapse of the lower electrode 162A. The capacitor dielectric layer 164may be conformally formed on the lower electrode 162A and the supportingmember 180. The capacitor dielectric layer 164 may have features similarto or the same as the capacitor dielectric layer 30, 30A, 30B, 30Cand/or 30D as described with reference to FIGS. 1 to 5. An upperelectrode 166A may be formed on the capacitor dielectric layer 164 tofill a space between the adjacent lower electrodes 162A.

In some embodiments, in the semiconductor device 100A according to theexample embodiment, although a thickness of the capacitor dielectriclayer 164 is small, the capacitor structure may have a high capacitanceand a leakage current or a short circuit between the lower and secondelectrodes 162A and 166A through the capacitor dielectric layer 164 maybe reduced or prevented from occurring.

FIG. 8 is a flow-chart diagram illustrating a method of manufacturing acapacitor structure according to example embodiments of the inventiveconcepts.

FIGS. 9A and 9B are cross-sectional views illustrating operations orstages of a method of manufacturing a capacitor structure according toexample embodiments of the inventive concepts. FIGS. 9A and 9B mayillustrate a method of the manufacturing the capacitor structure 10 asdescribed with reference to FIG. 1.

Referring to FIGS. 8 and 9A, in operation S10, a first electrode 22 maybe formed on a substrate.

In some embodiments, the first electrode 22 may be formed of one or moreof doped polysilicon, metal such as ruthenium (Ru), iridium (Ir),titanium (Ti), tantalum (Ta), tungsten (W), conductive metal nitridesuch as titanium nitride (TiN), tantalum nitride (TaN), tungsten nitride(WN), and conductive metal oxide such as iridium oxide, etc. Forexample, the first electrode 22 may be formed by a LPCVD process, aPECVD process, a UHV-CVD process, an ALD process, a metal organic CVD(MOCVD) process, or a metal organic ALD (MOALD) process.

A first interface layer 52 may be formed on the first electrode 22. Thefirst interface layer 52 may include an electrically conductivetransition metal oxide, e.g., titanium oxide (TiO_(x). 0<x<2), titaniumaluminum oxide (TiAlP_(x)), manganese oxide (MnO_(x), 0<x<2), or TiON,and may be formed to a thickness of about 1 Å to about 10 Å.

In operation S20, a base layer 42 may be formed, using a firstdielectric material, on the first electrode 22 on which the firstinterface 52 is formed.

In some embodiments, the base layer 42 may be formed by a LPCVD process,a PECVD process, a UHV-CVD process, an ALD process, a MOCVD process, ora MOALD process. The first dielectric material may be a high-kdielectric material such as metal oxide and may have a dielectricconstant of about 4 to about 40. For example, the first dielectricmaterial may include one or more of zirconium oxide (ZrO₂), hafniumoxide (HfO₂), zirconium silicon oxide (ZrSiO_(x)), hafnium silicon oxide(HfSiO_(x)), zirconium hafnium silicon oxide (ZrHfSiO_(x)), aluminumoxide (Al₂O₃) and a combination thereof.

The base layer 42 may be formed to a first thickness T1 along a seconddirection D2 vertical or perpendicular to a top surface of the firstelectrode 22, and the first thickness T1 may range from about 10 Å toabout 200 Å, but not limited thereto.

The base layer 42 may include a plurality of crystal grains GR. Thecrystal grains GR may have or may extend with the first thickness Ti inthe second direction D2. A boundary or an interface between the crystalgrains GR may be referred to as a grain boundary GB. In embodiments inwhich the base layer 42 includes a material having a high surfaceroughness, the base layer 42 may have an uneven, discontinuous topsurface profile around the grain boundary GB.

Referring to FIGS. 8 and 9B, in operation S30, a dielectric particlelayer 44 may be formed at or along at least a portion of the grainboundary GB using the second dielectric material.

In some embodiments, the second dielectric material may be differentfrom the first dielectric material. The second dielectric material mayhave a high band gap energy (Eg), such as silicon oxide or metal oxide,and a smaller dielectric constant than the first dielectric material.For example, the second dielectric material may have the dielectricconstant of about 3.9 to about 40 and the band gap energy (Eg) of about5 to about 10 Ev. In some embodiments, the second dielectric materialinclude one or more of aluminum oxide (AL₂O₃), Beryllium oxide (BeO),boron oxide (B₂O₃), silicon oxide (SiO₂), scandium oxide (Sc₂O₃),yttrium oxide (Y₂O₃), lanthanum oxide (La₂O₃), zirconium hafnium siliconoxide (ZrHfSiOx), aluminum nitride (AlN), boron nitride (BN), siliconnitride (Si₃N₄) or combinations thereof, but not limited thereto.

In some embodiments, the dielectric particle layer 44 may be formed by aLPCVD process, a PECVD process, a UHV-CVD process, an ALD process, aMOCVD process, or a MOALD process at a low pressure and low temperatureatmosphere. For example, the dielectric particle layer 44 may be formedat a temperature of about 0° C. to about 350° C. and at a pressure ofabout 80 Pa to about 200 Pa, but not limited thereto.

In some embodiments, the dielectric particle layer 44 may be formed byrepeating a plurality of times a deposition cycle including supplying aprecursor including the second dielectric material, purging, supplying areactant gas, and purging. In other embodiments, the dielectric particlelayer 44 may be formed by repeating a plurality of times a depositioncycle including a first supply of the precursor, a purge, a secondsupply of the precursor, a purge, a first supply of the reactant gas,purge, a second supply of the reactant gas, and purge. However, aspectsof the inventive concepts are not limited thereto.

In some embodiments, the precursor may include trimethylaluminum (TMA),triethyaluminum (TEA), trimethylborane (TMB) or triethylborane (TEB),but not limited thereto.

As shown in FIG. 9B, the dielectric particle layer 44 may includedielectric nanoparticles dispersed at the grain boundary of the baselayer 42. That is, the dielectric material particles may contact thegrain boundary GB of the base layer 44 and may be disposed adjacent tothe grain boundary GB. The dielectric nanoparticles may be disposed on atop surface of the base layer 42. Some of the dielectric nanoparticlesin the dielectric particle layer 44 may be in contact with each otherand may agglomerate each other. Some of the dielectric nanoparticles mayrandomly be dispersed.

In some embodiments, the dielectric nanoparticles have a diameter ofabout 1 Å to 10 Å and may have a spherical shape, a hemispherical shape,an elliptical shape or a dot-shape. The dielectric nanoparticles may bepreferentially formed along the grain boundary GB, and thus thecapacitor dielectric layer 30 including the base layer 42 and thedielectric particle layer 44 may have a flat or substantially planar topsurface profile.

Next, referring to FIGS. 8 and 1, in operation S40, a second electrode24 may be formed on the base layer 42 and the dielectric particle layer44.

The second electrode 24 may be formed of one or more of dopedpolysilicon, metal such as ruthenium (Ru), iridium (Ir), titanium (Ti),tantalum (Ta), tungsten (W), conductive metal nitride such as titaniumnitride (TiN), tantalum nitride (TaN), tungsten nitride (WN), andconductive metal oxide such as iridium oxide, etc. For example, thesecond electrode 22 may be formed by a LPCVD process, a PECVD process, aUHV-CVD process, an ALD process, a MOCVD process, or a MOALD process.

Before forming the second electrode 24, a second interface layer 54 maybe selectively formed on the base layer 42 and the dielectric particlelayer 44. The second interface layer 54 may be formed by a processsimilar to the process of forming the first interface layer 52. Thesecond interface layer 54 may act as a barrier layer to reduce orprevent oxygen atoms in the base the base layer 42 and the dielectricparticle layer 44 form diffusing into the second electrode 24 whileforming the second electrode 24.

The capacitor structure 10 may be formed by the above-describedprocesses.

According to some methods of manufacturing the capacitor structure 10,the dielectric particle layer 44 including the dielectric nanoparticlesmay be formed at the grain boundary GB of the base layer 42. Thedielectric nanoparticles may be disposed in a space between the crystalgrains GR of the base layer 42 and may continuously extend along athickness direction of the capacitor dielectric layer 30. Thus, thecapacitor structure 10 may have a high capacitance although thethickness T1 of the capacitor dielectric layer 30 is small.

Further, although the base layer 42 has a high surface roughness, thenanoparticles may be disposed in the space between the crystal grains GRsuch that the capacitor dielectric layer 30 may have a flat orsubstantially planar top surface profile and a low surface roughness.Accordingly, a leakage current or a short circuit between the first andsecond electrodes 22 and 24 through the capacitor dielectric layer 30may be reduced or prevented from occurring and a breakdown of thecapacitor dielectric layer 30 may also be reduced or prevented fromoccurring.

FIG. 10 is a flow-chart diagram illustrating a method of manufacturing acapacitor structure according to example embodiments of the inventiveconcepts;

FIGS. 11A and 11B are cross-sectional views illustrating operations orstages of a method of manufacturing a capacitor structure according toexample embodiments of the inventive concepts. In FIGS. 11A and 11B, thesame reference numerals denote the same elements as in FIGS. 1 to 9B.

Referring to FIGS. 10 and 11A, in operation S10A, a first electrode 22may be formed on a substrate.

In operation S20A, a base layer 42 may be formed on the first electrode22 using a first dielectric material. The base layer 42 may include aplurality of crystal grains GR extending a second direction D2 verticalor perpendicular to a top surface of the first electrode 22. A topsurface 52T of a first interface layer 52 may be exposed between thecrystal grains GR (or the top surface of the first electrode 22 may beexposed between the crystal grains GR in embodiments in which the firstinterface 52 is not formed).

Referring to FIGS. 10 and 11B, in operation S30A, a dielectric particlelayer 44 may be formed at or extending along at least a portion of agrain boundary GB of the base layer 42 using a second dielectricmaterial.

In some embodiments, the dielectric particle layer 44 may be formed tohave a pillar shaped cross-section and extend in the second direction D2(e.g., a thickness direction of the base layer 42). A bottom surface ofthe dielectric particle layer 44 may contact the top surface 52T of thefirst interface layer 52 (or the first electrode 22 in embodiments wherethe first interface layer 52 is not present).

In some embodiments, the dielectric particle layer 44 may be formedusing a material having an improved gap-fill property as the seconddielectric material, and thus may fill a space between the crystalgrains GR of the base layer 42 without a void. In other embodiments, thedielectric particle layer 44 may be formed by a flowable CVD process andthe following annealing process to fill the space between the crystalgrains GR without the void. However, aspects of the present inventiveconcepts are not limited thereto.

After selectively controlling a surface roughness of the first interfacelayer 52, the base layer 42 may be formed on the first interface layer52 such that the top surface 52T of the first interface layer 52 isexposed in the space between the crystal grains GR of the base layer 42.Next, the dielectric particle layer 44 may be formed to fill the spacebetween the crystal grains GR of the base layer 42.

Depending on morphology or a surface roughness of the crystal grains GRof the base layer 42, a width between the crystal grains GR may be thesame or vary along the thickness direction of the base layer 42. Forexample, the crystal grains GR of the base layer 42 may bepreferentially formed along the second direction D2, and thus the spacebetween the crystal grains GR may be substantially uniform or may havesubstantially the same width. In this case, the dielectric particlelayer 44A described with reference to FIG. 2 may be formed to have asubstantially uniform width W1 (refer to FIG. 2) along the thicknessdirection of the base layer 42 and a pillar shaped cross-section. Insome embodiments, when the surface roughness of the base layer 42 ishigh, a width W3 (refer to FIG. 3) between the crystal grains GR of anupper portion of the base layer 42 may be greater than a width W2 (referto FIG. 3) between the crystal grains GR of a lower portion of the baselayer 42. In this case, the dielectric particle layer 44B described withreference to FIG. 3 may be formed to have a width varying along thethickness direction of the base layer 42 and a pillar shapedcross-section.

Next, in operation S40A, a second electrode 24 (refer to FIG. 3) may beformed on the base layer 42 and the dielectric particle layer 44.

FIG. 12 is a flow-chart diagram illustrating a method of manufacturing acapacitor structure according to example embodiments of the inventiveconcepts;

FIGS. 13A to 13C are cross-sectional views illustrating operations orstages of a method of manufacturing a capacitor structure according toexample embodiments of the inventive concepts. In FIGS. 13A to 13C, thesame reference numerals denote the same elements as in FIGS. 1 to 11B.

Referring to FIGS. 12 and 13A, in operation SlOB, a first electrode 22may be formed on a substrate.

In operation S20B, a base layer 42 may be formed on the first electrode22 using a first dielectric material.

In some embodiments, the base layer 42 may be formed by a processperformed at a relatively low pressure and a relatively low temperature.Thus, a width or a diameter of the crystal grains GRa of the base layer42 in a first direction D1 may be small, and/or crystallinity of thecrystal grains GRa of the base layer 42 may be low. Also, grainboundaries GBa between the crystal grains GRa may be formed in a higherdensity. However, aspects of the inventive concepts are not limitedthereto.

Referring to FIGS. 12 and 13B, in operation S50B, an annealing processon the substrate may be performed.

The annealing process may be performed at about 100° C. to about 1000°C. for several seconds to several hours. The annealing process mayinclude a rapid thermal annealing (RTA) process or a laser annealingprocess, but embodiments of the inventive concepts are not limitedthereto.

By the annealing process, a size of the crystal grains GR of the baselayer 42 may be increased. For example, the crystal grains GRa (refer toFIG. 13A) having a small width or a small diameter may be merged withthe adjacent crystal grains GRa such that larger crystal grains GR maybe grown. Thus, according to the growth of the crystal grains GR, thegrain boundary GB may be relocated. For example, as shown in FIG. 13B,according to the growth of the crystal grains GR, a space between thecrystal grains GR may be enlarged, and thus a top surface 52T of a firstinterface layer 52 may be exposed.

Referring to FIGS. 12 and 13C, in operation S30B, a dielectric particlelayer 44 may be formed in the base layer 42 using a second dielectricmaterial. As described with reference to FIG. 11B, the dielectricparticle layer 44 may have a substantially uniform width in a thicknessdirection of the base layer 42 and a pillar shaped cross-section. Insome embodiments, the dielectric particle layer 44 may have a pillarshaped cross-section of which an upper width is larger than a lowerwidth.

Next, in operation S40B, a second electrode 24 (refer to FIG. 3) may beformed on the base layer 42 and the dielectric particle layer 44.

FIG. 14 is a flow-chart diagram illustrating a method of manufacturing acapacitor structure according to example embodiments of the inventiveconcepts;

FIGS. 15A and 15B are cross-sectional views illustrating operations orstages of a method of manufacturing a capacitor structure according toexample embodiments of the inventive concepts. In FIGS. 15A and 15B, thesame reference numerals denote the same elements as in FIGS. 1 to 13C.

Referring to FIGS. 14 and 15A, a first electrode 22 may be formed on asubstrate (operation S10C), a first base layer 42 may be formed on thefirst electrode 22 using a first dielectric material (operation S20C1),and a first dielectric particle layer 44 may be formed at or extendingalong at least a portion of a grain boundary GB of the first base layer42 using a second dielectric material (operation S30C1). Here, the firstbase layer 42 and the first dielectric particle layer 44 may be referredto as a first dielectric layer 32.

Further details of the formation of the first dielectric layer 32 mayrefer the detailed descriptions with reference to FIGS. 8 to 9B.

Next, in operation S20C2, a second base layer 46 may be formed on thefirst base layer 42 and the first dielectric particle layer 44. Here,the first dielectric layer 32 may include the first base layer 42 andthe first dielectric particle layer 44, and thus may have a flat orsubstantially planar top surface profile. For example, since the firstdielectric particle layer 44 may include dielectric nanoparticlesarranged to continuously or substantially continuously extend along agrain boundary GB of the first base layer 42, the first dielectric layer32 may have a low surface roughness of about 0.3 nm or less.

The second base layer 46 may be formed by a process similar to theprocess of forming the first base layer 42. The second base layer 46 maybe formed to have an improved crystallinity because the second baselayer 46 is formed on the first dielectric layer 32 having the lowsurface roughness.

Referring to FIGS. 14 and 15B, in operation S30C2, a second dielectricparticle layer 48 may be formed at or extending along at least a portionof a grain boundary GB of the second base layer 46 using the seconddielectric material.

Here, the second base layer 46 and the second dielectric particle layer48 may be referred to as a second dielectric layer 34. The seconddielectric particle layer 48 may be formed by a process similar to theprocess of forming the first dielectric particle layer 44. In someembodiments, a first thickness T1 of the first dielectric layer 32 maybe equal to or different from a second thickness T2 of the seconddielectric layer 34.

As a result, a capacitor dielectric layer 30C including stacked firstand second dielectric layers 32 and 34 may be formed.

Next, in operation S40C, a second electrode 24 (refer to FIG. 4) may beformed on the second base layer 46 and the second dielectric particlelayer 48.

As shown in FIGS. 15A and 15B, the first and second dielectric particlelayers 44 and 48 may include the dielectric nanoparticles, butembodiments of the inventive concepts are not limited thereto. Forexample, one or more of the first second dielectric particle layers 44and 48 may be formed to have a pillar shaped cross-section continuouslyfilling spaces between the crystal grains GR of the base layers 42 and46.

FIG. 16 is a flow-chart diagram illustrating a method of manufacturing acapacitor structure according to example embodiments of the inventiveconcepts;

FIGS. 17A and 17B are cross-sectional views illustrating operations orstages of a method of manufacturing a capacitor structure according toexample embodiments of the inventive concepts. In FIGS. 17A and 17B, thesame reference numerals denote the same elements as in FIGS. 1 to 15B.

Referring to FIGS. 16 and 17A, a first electrode 22 may be formed on asubstrate (operation S10D), and a first base layer 42 may be formed onthe first electrode 22 using a first dielectric material (operationS20D1).

Next, in operation S20D2, the second base layer 46 may be formed usingthe first dielectric material. The second base layer 46 may be formed bya process similar to the process of forming the first base layer 42.

In the process of forming the second base layer 46, a space betweencrystal grains GR of the first base layer 42 may not be partiallyfilled, and thus a void may be formed at a portion of the space of thecrystal grains GR of the first base layer 42. Further, a grain boundaryGB of the second base layer 46 may be disposed adjacent to a grainboundary GB of the first base layer 42. For example, since the firstbase layer 42 may have an uneven, discontinuous top surface profilearound the grain boundary GB, a growth of the crystal grain GR of thesecond base layer 46 on the grain boundary GB of the first base layer 42may be suppressed. However, aspects of the present inventive conceptsare not limited thereto.

Referring to FIGS. 16 and 17B, in operation S30D2, a second dielectricparticle layer 48 including dielectric nanoparticles may be formed at orextending along at least a portion of a grain boundary GB of the secondbase layer 46 using a second dielectric material.

In some embodiments, the second dielectric particle layer 48 may beformed by a process similar to the process of forming the dielectricparticle layer 44 as described with reference to FIGS. 8 and 9B.

In the process of forming the second dielectric particle layer 48, thedielectric nanoparticles may diffuse or move along the space between thecrystal grains GR of the second base layer 46, and thus may be disposedat the grain boundary GB of an upper portion of the first base layer 42such that a first dielectric particle layer 44 may be formed.

As shown in FIG. 17B, the first dielectric particle layer 44 may bedisposed at only the grain boundary GB of the upper portion of the firstbase layer 42. For example, the first dielectric particle layer 44 maybe formed only up to a predetermined height from a top surface of thefirst dielectric layer 32 but may not be formed at the grain boundary GBof a lower portion of the first base layer 42.

As a result, a capacitor dielectric layer 30D including the stackedfirst and second dielectric layers 32 and 34 may be formed.

FIGS. 18A to 18H are cross-sectional views illustrating operations orstages of a method of manufacturing a semiconductor device 100 accordingto example embodiments of the inventive concepts. The manufacturingmethod may be a method of manufacturing the semiconductor device 100 asdescribed with reference to FIGS. 6A and 6B.

Referring to FIG. 18A, a trench 108 may be formed in a substrate 102including an active region 106 to extend in an X direction (refer toFIG. 6A) parallel to a top surface of the substrate 102 and cross theactive region 106.

An isolation trench 104T is formed in the substrate 102, and anisolation layer 104 may be formed in the isolation trench 104T. Theactive region 106 may be defined in the substrate 102 by the isolationlayer 104. The active region 10 may have a long island shape that has ashort axis and a long axis as the active region 106 shown in FIG. 6A.Further details of the substrate 102 may be the same as described withreference to FIGS. 6A and 6B. The isolation layer 104 may include asingle insulating layer or multiple layers formed of a combination of atleast two types of insulating layers.

In some embodiments, first and second source/drain regions 109A and 109Bmay be formed in an upper portion of the active region 106 by implantingimpurity ions in the substrate 102. In other embodiments, after forminga gate structure 120 filling the trench 108, the source/drain regions109A and 109B may be formed at opposite sides of the gate structure 120.

A first mask may be formed on the substrate 102, and then the trench 108may be formed in the substrate 102 by etching the substrate 102 usingthe first mask as an etch mask. A plurality of the trenches 108 may beformed to extend parallel to each other, and each trench 108 may have alinear shape crossing the active region 106.

In some embodiments, by etching the substrate 102 and the isolationlayer 104 using an etching condition in which an etch depth of thesubstrate 102 is different from an etch depth of the isolation layer104, a bottom surface of the trench 108 may be formed to have a step. Insome embodiments, to form the trench 108 having the stepped bottomsurface, the isolation layer 104 and the substrate 102 may be etchedusing separate etching processes such that the etch depth of theisolation layer 104 may be different from the etch depth of thesubstrate 102.

Next, a gate insulating layer 122 may be formed on a bottom surface andan inner wall of the trench 108. The gate insulating layer 122 mayinclude one or more of silicon oxide, silicon nitride, siliconoxynitride and a high-k dielectric material having a dielectric constantgreater than silicon oxide.

After forming a gate conductive layer filling the trench 108, an upperportion of the gate conductive layer may be etched by an etch-backprocess to form a gate electrode 124. In some embodiments, the gateelectrode 124 may include a work function adjustment layer formed on thegate insulating layer 122 and a buried metal layer formed on the workfunction adjustment layer to fill a lower portion of the trench 108. Thework function adjustment layer may include metal, metal nitride, and/ormetal carbide, such as Ti, TiN, TiAlN, TiAlC, TiAlCN, TiSiCN, Ta, TaN,TaAlN, TaAlCN, TaSiCN. The buried metal layer may include one or more ofW, WN, TiN and TaN.

Next, an insulating material may be formed to fill a remaining portionof the trench 108, and the insulating material may be planarized untilthe top surface of the substrate 102 is exposed such that a gate cappinglayer 126 may be formed on the inner wall of the trench 108. Further,the first mask may be removed.

Referring to FIG. 18B, a first insulating interlayer 142 may be formedon the substrate 102, and an opening exposing the first source/drainregion 109A may be formed in the first insulating interlayer 142. Aconductive layer may be formed on the insulating layer 142 to fill theopening, and the conductive layer may be planarized such that a bit linecontact 132 is formed in the opening to be electrically connected to thefirs source/drain region 109A.

Next, a first bit line 134 and a bit line capping layer 136 may beformed on the first insulating interlayer 142 to extend in a Y direction(refer to FIG. 6A) parallel to the top surface of the substrate 102 andvertical or perpendicular to the X direction. In some embodiments, a bitline spacer may be formed on sidewalls of the first bit line 134 and thebit line capping layer 136 and may further include an air space.

Referring to FIG. 18C, a second insulating interlayer 144 may be formedon the first insulating interlayer 142 to extend on or cover the bitline 134 and the bit line capping layer 136. A top surface of the secondinsulating interlayer 144 may be positioned at a level equal to orhigher than a top surface of the bit line capping layer 136.

Next, an opening may be formed in the first and second insulatinginterlayers 142 and 144 to expose the second source/drain region 109B,and a contact structure 146 may be formed in the opening. For example, alower contact pattern, a metal silicide layer, a barrier layer and anupper contact pattern may be sequentially formed in the opening suchthat the contact structure 146 may be formed to be electricallyconnected to the second source/drain region 109B.

Referring to FIG. 18D, after sequentially forming an etch stop layer 150and a mold layer 210 on the second insulating interlayer 144 and thecontact structure 146, openings 210H and 150T may be formed in the moldlayer 210 and the etch stop layer 150. The openings 210H and 150T may beintegrally connected to each other and may expose a top surface of thecontact structure 146.

In some embodiments, the mold layer 210 and the etch stop layer 150 mayinclude materials having an etch selectivity with respect to each other.For example, when the mold layer 210 may include silicon oxide, the etchstop layer 150 may include silicon nitride. In some embodiments, themold layer 210 may be formed of multiple layers including materialshaving different etch rates.

Referring to FIG. 18E, a lower electrode 162 may be formed on the moldlayer 210 and the etch stop layer 150 to conformally extend on or coverinner surfaces of the openings 150T and 201H. The lower electrode 162may be formed by a process similar to the process of forming the firstelectrode 22 as described with respect to FIGS. 8 and 9A.

Referring to FIG. 18F, a portion of the lower electrode 162 on a topsurface of the mold layer 210 may be removed by an etch-back process ora chemical mechanical polishing process.

Referring to FIG. 18G, the mold layer 210 may be removed.

In the removal process of the mold layer 210, the etch stop layer 150may remain without being removed. The lower electrode 162 may bedisposed on the contact structure 146 and may be formed in a cylindricalshape having a closed bottom.

Referring to FIG. 18H, a capacitor dielectric layer 164 may be formed onthe etch stop layer 150 and the lower electrode 162. The capacitordielectric layer 164 may be formed by a process similar to the processof forming the capacitor dielectric layer 30 as described with respectto FIGS. 8 and 9A.

In some embodiments, the capacitor dielectric layer 164 may include abase layer 164_1 (refer to FIG. 6B) and a dielectric particle layer164_2 (refer to FIG. 6B) at least partially continuously extending alonga thickness direction of the capacitor dielectric layer 164 at a grainboundary of the base layer 164_1. The dielectric particle layer 164_2may include dielectric nanoparticles disposed in a space between crystalgrains of the base layer 164_1. In some embodiments, the capacitordielectric layer 164 may have features similar to or the same as thecapacitor dielectric layers 30A, 30B, 30C and/or 30D as described withreference to FIGS. 2 to 5.

Referring again to FIG. 6B, an upper electrode 166 may be formed on thecapacitor dielectric layer 164.

The semiconductor device 100 may be formed through the above-describedprocesses.

In general, as the semiconductor device is scaled down, a diameter ofthe lower electrode 162 may be reduced and an aspect ratio of the lowerelectrode 162 may be increased. Further, the capacitor dielectric layer164 that is conformally formed on an inner wall of the lower electrode164 may be thinner. As described above with reference to FIGS. 1 to 5,since the capacitor dielectric layer 164 includes the base layer 164_1and the dielectric particle layer 164_2, the capacitor dielectric layer164 may have a high capacitance even at a relatively small thickness.Additionally, the capacitor dielectric layer 164 may have a low surfaceroughness, and thus a short circuit or a leakage current between theupper and lower electrodes 166 and 162 through the capacitor dielectriclayer 164 may be reduced or prevented from occurring.

FIGS. 19A to 19E are cross-sectional views illustrating operations orstages of a method of manufacturing a semiconductor device 100Aaccording to example embodiments of the inventive concepts. Themanufacturing method may be a method of manufacturing the semiconductordevice 100A as described with reference to FIG. 7.

First, by performing the process as described with reference to FIGS.18A to 18C, a structure in which a second insulating interlayer 144 anda contact structure 146 is formed may be obtained.

Referring to FIG. 19A, an etch stop layer 150, a first mold layer 220, asupporting member 180 and a second mold layer 230 may be sequentiallyformed on the second insulating interlayer 144 and the contact structure146.

In some embodiments, the first and second mold layers 220 and 230 andthe etch stop layer 150 may include materials having an etch selectivitywith respect to each other. Further, the first and second mold layers220 and 230 and the supporting member 180 may include materials havingan etch selectivity with respect to each other. The first and secondmold layers 220 and 230 may include the same material or differentmaterials. For example, the first and second mold layers 220 and 230 mayinclude silicon oxide, and the etch stop layer 150 and the supportingmember 180 may include silicon nitride.

Referring to FIG. 19B, an opening 230H penetrating the second mold layer230, the supporting member 180 and the first mold layer 220 and anopening 150T penetrating the etch stop layer 150 may be sequentiallyformed. The openings 230H and 150T may be integrally connected to eachother and may expose a top surface of the contact structure 146. A sidewall of the supporting member 180 may be exposed on an inner wall of theopening 230H.

Referring to FIG. 19C, a lower electrode layer may be formed on thesecond mold layer 230 to fill the openings 150T and 230H, and then anupper portion of lower electrode layer may be etched-back to expose atop surface of the second mold layer 230 such that a lower electrode162A may be formed in the openings 150T and 230H.

The lower electrode 162A may be formed in a pillar shape filling theopenings 150T and 230H. A sidewall of the lower electrode 162A maycontact the supporting member 180.

Referring to FIG. 19D, the first and second mold layers 220 and 230 maybe removed.

First, the second mold layer 230 may be removed, and then afterperforming a patterning process for forming an opening region in thesupporting member 180, the first mold layer 220 may be removed throughthe opening region. However, aspects of the present inventive conceptsare not limited thereto. For example, during the process of forming thesupporting member 180, the patterning process for forming the openingregion may also be performed.

In the removal process of the first and second mold layers 220 and 230,the supporting member 180 may remain without being fully removed. Thesupporting member 180 may be disposed between the lower electrodes 162A,thereby preventing collapse or leaning of the lower electrode 162A.

Referring to FIG. 19E, a capacitor dielectric layer 164 may be formed onthe etch stop layer 150 and the lower electrode 162A. The capacitordielectric layer 164 may also be conformally formed on the supportingmember 180. The capacitor dielectric layer 164 may be formed by aprocess similar to the process for forming the capacitor dielectriclayer 30 as described with reference to FIGS. 8 and 9A.

Referring again to FIG. 7, an upper electrode 166A may be formed on thecapacitor dielectric layer 164.

The semiconductor device 100A may be formed through the above-describedprocesses.

While the present inventive concepts have been particularly shown anddescribed with reference to example embodiments thereof, it will beunderstood by those of ordinary skill in the art that various changes inform and details may be made therein without departing from the spiritand scope of the present disclosure as defined by the following claims.

What is claimed is:
 1. A capacitor structure for a semiconductor devicecomprising: a lower electrode on a substrate; a capacitor dielectriclayer on a top surface of the lower electrode; and an upper electrode onthe capacitor dielectric layer, wherein the capacitor dielectric layercomprises: a base layer comprising a first dielectric material; and aplurality of dielectric nanoparticles dispersed in the base layer, eachof the plurality of dielectric nanoparticles comprising a seconddielectric material which is different from the first dielectricmaterial, wherein a first density of dielectric nanoparticles dispersedin a first portion of the base layer is higher than a second density ofdielectric nanoparticles dispersed in a second portion of the baselayer, wherein the second portion of the base layer is closer to the topsurface of the lower electrode than the first portion of the base layer,and wherein a thickness of the capacitor dielectric layer is about 20Angstroms (Å) to 80 Å.
 2. The capacitor structure of claim 1, whereinthe base layer includes crystal grains, and the plurality of dielectricnanoparticles fill at least a portion of grain boundary space formedbetween the crystal grains.
 3. The capacitor structure of claim 2,wherein each of the dielectric nanoparticles has a diameter of about 1 Åto 10 Å.
 4. The capacitor structure of claim 1, wherein a surfaceroughness of the capacitor dielectric layer is 0.3 nm or less.
 5. Acapacitor structure for a semiconductor device comprising: a lowerelectrode on a substrate; a capacitor dielectric layer on a top surfaceof the lower electrode; and an upper electrode on the capacitordielectric layer, wherein the capacitor dielectric layer comprises: abase layer comprising a first dielectric material; and a plurality ofdielectric nanoparticles dispersed in the base layer, each of theplurality of dielectric nanoparticles comprising a second dielectricmaterial which is different from the first dielectric material, whereina first density of dielectric nanoparticles dispersed in a first portionof the base layer is higher than a second density of dielectricnanoparticles dispersed in a second portion of the base layer, whereinthe second portion of the base layer is closer to the top surface of thelower electrode than the first portion of the base layer, wherein thefirst dielectric material comprises one or more material of zirconiumoxide (ZrO₂), hafnium oxide (HfO₂) , zirconium silicon oxide(ZrSiO_(x)), hafnium silicon oxide (HfSiO_(x)), and zirconium hafniumsilicon oxide (ZrHfSiO_(x)).
 6. The capacitor structure of claim 1,wherein the second dielectric material comprises one or more material ofAl₂O₃, BeO, B₂O₃, SiO₂, Sc₂O₃, Y₂O₃, La₂O₃, AlN, BN and Si₃N₄.
 7. Thecapacitor structure of claim 1, further comprising a dielectric cappinglayer conformally disposed between the base layer and the upperelectrode.
 8. The capacitor structure of claim 1, wherein the base layercomprises a first base layer and a second base layer which arevertically stacked, and are formed through separate process steps. 9.The capacitor structure of claim 8, wherein grain boundaries of crystalgrains have discontinuities at an interface between the first base layerand the second base layer.
 10. The capacitor structure of claim 9,further comprising a dielectric particle layer disposed at the interfacebetween the first base layer and the second base layer, wherein thedielectric particle layer comprises the second dielectric material. 11.A capacitor structure for a semiconductor device comprising: a lowerelectrode on a substrate; a capacitor dielectric layer on the lowerelectrode; and an upper electrode on the capacitor dielectric layer,wherein the capacitor dielectric layer comprises: a first base layer ona top surface of the lower electrode, the first base layer comprising afirst dielectric material; a second base layer on the first base layer,the second base layer comprising the first dielectric material; and aplurality of dielectric nanoparticles dispersed in the first base layerand the second base layer, each of the plurality of dielectricnanoparticles comprising a second dielectric material different from thefirst dielectric material, wherein a first density of dielectricnanoparticles dispersed in the first base layer is lower than a seconddensity of dielectric nanoparticles dispersed in the second base layer.12. The capacitor structure of claim 11, wherein a thickness of thecapacitor dielectric layer is about 20 Å to 80 Å.
 13. The capacitorstructure of claim 12, wherein the first base layer and the second baselayer include crystal grains respectively, and the plurality ofdielectric nanoparticles fill at least a portion of grain boundary spaceformed between the crystal grains.
 14. The capacitor structure of claim13, wherein grain boundaries of the crystal grains have discontinuitiesat an interface between the first base layer and the second base layer.15. The capacitor structure of claim 13, wherein each of the pluralityof dielectric nanoparticles has a diameter of about 1 Å to 10 Å.
 16. Thecapacitor structure of claim 11, wherein a surface roughness of thecapacitor dielectric layer is 0.3 nm or less.
 17. The capacitorstructure of claim 11, wherein the first dielectric material comprisesone or more material of zirconium oxide (ZrO₂), hafnium oxide (HfO₂),zirconium silicon oxide (ZrSiO_(x)), hafnium silicon oxide (HfSiO_(x)),and zirconium hafnium silicon oxide (ZrHfSiO_(x)).
 18. The capacitorstructure of claim 11, wherein the second dielectric material comprisesone or more material of Al₂O₃, BeO, B₂O₃, SiO₂, Sc₂O₃, Y₂O₃, La₂O₃, AlN,BN and Si₃N₄.
 19. The capacitor structure of claim 11, furthercomprising a dielectric capping layer conformally disposed between thefirst base layer and the upper electrode.